WO2022053420A1 - Procédé de préparation de composés fluoroéthers à groupes terminaux insaturés - Google Patents

Procédé de préparation de composés fluoroéthers à groupes terminaux insaturés Download PDF

Info

Publication number
WO2022053420A1
WO2022053420A1 PCT/EP2021/074444 EP2021074444W WO2022053420A1 WO 2022053420 A1 WO2022053420 A1 WO 2022053420A1 EP 2021074444 W EP2021074444 W EP 2021074444W WO 2022053420 A1 WO2022053420 A1 WO 2022053420A1
Authority
WO
WIPO (PCT)
Prior art keywords
process according
group
formula
compounds
optionally contains
Prior art date
Application number
PCT/EP2021/074444
Other languages
English (en)
Inventor
Reiner Friedrich
Fabian Koch
Laura SCHIMURA
Original Assignee
Merck Patent Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Merck Patent Gmbh filed Critical Merck Patent Gmbh
Priority to KR1020237010989A priority Critical patent/KR20230065282A/ko
Priority to EP21773347.6A priority patent/EP4211105A1/fr
Priority to JP2023515577A priority patent/JP2023540369A/ja
Priority to US18/024,617 priority patent/US20230365484A1/en
Priority to CN202180053388.XA priority patent/CN116096697A/zh
Publication of WO2022053420A1 publication Critical patent/WO2022053420A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
    • C07C319/08—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by replacement of hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/12—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
    • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/17—Unsaturated ethers containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/62—Halogen-containing esters
    • C07C69/65—Halogen-containing esters of unsaturated acids
    • C07C69/653—Acrylic acid esters; Methacrylic acid esters; Haloacrylic acid esters; Halomethacrylic acid esters

Definitions

  • the present invention relates to a process of preparing polyfluoroether compounds with unsaturated end groups and to compounds prepared by said process.
  • Dirt-repellent coatings are a vital part for many technical applications. Often fluorinated material are used, because they have the unique characteristics of providing oil and water repellency at the same time. Out-door equipment, technical protection clothing like fireman suits, bullet proofed jackets or scrubs are only a few examples for these applications.
  • For dirt repellent coatings polyfluoroether acrylate or methacrylate monomers are often used.
  • Rf is preferably selected from the following groups: CF 3 -(CF 2 ) 0-3 -, CF 3 -(CF 2 ) 0-3 -O-, CF 3 -(CF 2 ) 0-3 -O-(CF 2 ) 1-3 -, CF 3 -(CF 2 ) 0-3 -O-(CF 2 ) 1-3 -O-, CF 3 -(CF 2 ) 0-3 -O-(CF 2 ) 1-3 -O-, CF 3 -(CF 2 ) 0-3 -O-(CF 2 ) 1-3 -O-CF 2 -, CF 3 -(CF 2 ) 0-3 -O-(CF 2 -O) 1-8 - and CF 3 -(CF 2 ) 0-3 -O-(CF 2 -O) 1-8 -CF 2 -.
  • Rf is very preferably selected from the following groups: CF 3 -(CF 2 ) 1-2 -, CF 3 -(CF 2 ) 1-2 -O-, CF 3 -O-(CF 2 ) 1-3 -, CF 3 -O-(CF 2 ) 1-2 -O-, CF 3 -(CF 2 ) 1-2- O-CF 2 -, CF 3 -O-(CF 2 ) 1-2 -O-CF 2 -, CF 3 -O-(CF 2 -O) 1-8 - and CF 3 -O-(CF 2 -O) 1-8 -CF 2 -.
  • Rf is preferably selected from the following groups: -(CF 2 ) 1-4 -, -O-(CF 2 ) 1-3 -O-, -(CF 2 ) 1-3 -(CF 2 ) 0-3 -O-(CF 2 ) 1-3 -, -O-(CF 2 ) 1-3 -(CF 2 ) 0-3 -O-(CF 2 ) 1-3 -O-, -(CF 2 ) 1-3 -O-(CF 2 ) 1-3 -O-CF 2 -, -CF 2 -(CF 2 ) 0-3 -O-(CF 2 -O) 1-8 - and CF 2 -(CF 2 ) 0-3 -O-(CF 2 -O) 1-8 -CF 2 -.
  • Rf is very preferably selected from the following groups: -(CF 2 ) 1-3 -, -(CF 2 ) 1-3 -O-, -O-(CF 2 ) 1-3 -O-, -CF 2 -O-(CF 2 ) 1-2 -O-, -CF 2 -(CF 2 ) 1-2- O-CF 2 -, -CF 2 -O-(CF 2 ) 1-2 -O-CF 2 -, -CF 2 -O-(CF 2 -O) 1-8 - and -CF 2 -O-(CF 2 -O) 1-8 -CF 2 -.
  • X is preferably an acrylate or methacrylate group, further preferably an ethynyl (i.e. -C ⁇ CH) group.
  • the valence of the group L is given by the sum of n+k and is thus 2, 3, 4, 5 or 6.
  • L is a divalent, trivalent or tetravalent group.
  • L is selected from a single bond or a saturated, straight-chain or branched, optionally hetero atoms, especially O and/or S atoms, and/or functional groups containing, organic group, especially preferably an alkylene group.
  • L is a saturated C1-C20, more preferably C1-C12, most preferably C1-C6, alkylene group that is straight-chain or branched, optionally contains one or more heteroatoms, preferably one or more O atoms, and optionally contains one or more functional groups.
  • Suitable and preferred functional groups include, without limitation, OH, epoxy, -Si(OMe) 3 ,-Si(OEt) 3 , CO 2 H or tertiary amino groups.
  • L is selected from the group consisting of methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, sec-butylene, t- butylene, or pentylene or hexylene which are straight-chain or branched.
  • L is a C1-C6 alkylene group that is straight-chain or branched and optionally contains one or more hetero atoms, preferably one or more O atoms, and optionally contains a functional group.
  • Especially preferred compounds of formula I are selected from the following formulae
  • i 2-10.
  • Especially preferred compounds of formula II are selected from the following formulae.
  • Especially preferred compounds of formula III are selected from the following formulae.
  • the process according to the present invention can be carried out using reactants and conditions that are known to the person skilled in the art and are described in the literature.
  • the necessary starting materials are commercially available, can be prepared by known processes from commercially available products or can be prepared analogously by known syntheses. Further suitable and preferred reactants and reaction conditions are described in the examples.
  • the reaction of compounds II and III is preferably carried out in an organic solvent. Suitable and preferred solvents include linear or cyclic alkyl ethers like dioxane, tetrahydrofurane or methyl-tert-butylether, or mixtures thereof, furthermore aliphatic hydrocarbons or aromatic hydrocarbons like toluene.
  • the reaction of compounds II and III is carried out in the presence of a base.
  • Suitable and preferred bases include alkali carbonates like Cs 2 CO 3 , alkaline earth carbonates like CaCO 3 , or alkali hydroxides, like KOH or NaOH.
  • the reaction mixture is preferably heated to a temperature above room temperature, preferably to a temperature of at least 50°C, more preferably at least 80°C, and stirred for a given time, preferably 12h or more.
  • the heating and stirring are preferably carried out in an inert reaction atmosphere like N 2 or Ar.
  • the final product can be isolated from the reaction mixture and purified by standard work up procedures that are well known to the skilled person and described in the literature, like distillation, extraction, filtering, washing, drying etc. Unless stated otherwise, above and below all percentages of solids are per cent by weight ("wt.
  • Example 1 Compound (1) is prepared as follows.
  • Example 2 Compound (2) is prepared as follows. In 150 ml stainless steel pressure reactor 7.96 g (0.03 mol) of Perfluoro propylvinyl ether (PPVE) was added to a solution consisting of 2.52.g (0,04 mol) 3-Butin-1-ol, 2.18 g (0.04 mol) KOH and 25 ml of 1,4 Dioxane. The mixture was heated to 75 °C and kept at this temperature for 20 h. For the work up the reaction mixture was diluted with 30 ml water and 30 ml MTBE, the organic layer was separated and the aqueous layer washed twice with 30 ml MTBE.
  • PPVE Perfluoro propylvinyl ether

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de préparation de composés polyfluoroéther à groupes terminaux insaturés et des composés préparés par ledit procédé.
PCT/EP2021/074444 2020-09-09 2021-09-06 Procédé de préparation de composés fluoroéthers à groupes terminaux insaturés WO2022053420A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
KR1020237010989A KR20230065282A (ko) 2020-09-09 2021-09-06 불포화 말단 기를 갖는 플루오로에테르 화합물의 제조 방법
EP21773347.6A EP4211105A1 (fr) 2020-09-09 2021-09-06 Procédé de préparation de composés fluoroéthers à groupes terminaux insaturés
JP2023515577A JP2023540369A (ja) 2020-09-09 2021-09-06 不飽和の末端基をもつフルオロエーテル化合物を調製するプロセス
US18/024,617 US20230365484A1 (en) 2020-09-09 2021-09-06 Process of preparing fluoroether compounds with unsaturated end groups
CN202180053388.XA CN116096697A (zh) 2020-09-09 2021-09-06 制备具有不饱和端基的氟醚化合物的方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP20195200 2020-09-09
EP20195200.9 2020-09-09

Publications (1)

Publication Number Publication Date
WO2022053420A1 true WO2022053420A1 (fr) 2022-03-17

Family

ID=72432804

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2021/074444 WO2022053420A1 (fr) 2020-09-09 2021-09-06 Procédé de préparation de composés fluoroéthers à groupes terminaux insaturés

Country Status (6)

Country Link
US (1) US20230365484A1 (fr)
EP (1) EP4211105A1 (fr)
JP (1) JP2023540369A (fr)
KR (1) KR20230065282A (fr)
CN (1) CN116096697A (fr)
WO (1) WO2022053420A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5052019A (fr) * 1973-09-13 1975-05-09
US20050113609A1 (en) * 2002-07-03 2005-05-26 Asahi Glass Company Limited Fluorine-containing unsaturated compound and method for its production
US20070299276A1 (en) * 2006-06-22 2007-12-27 Andrew Edward Feiring Preparation of fluoroalkoxystyrenes
US20140135518A1 (en) * 2012-11-14 2014-05-15 E I Du Pont De Nemours And Company Perfluoropolyvinyl modified aryl intermediates and monomers
WO2016032739A1 (fr) * 2014-08-27 2016-03-03 3M Innovative Properties Company Nouveaux alcènes polyfluoroalkylés et composés de silicium préparés à partir de ces derniers
WO2016096129A1 (fr) * 2014-12-19 2016-06-23 Merck Patent Gmbh Composés fluorés
WO2019049754A1 (fr) * 2017-09-05 2019-03-14 Ａｇｃ株式会社 Composé contenant du fluor, composition et article
WO2019067408A1 (fr) * 2017-09-27 2019-04-04 Arkema Inc. Polymères de (méth)acrylates d'éther d'haloalkyle et d'haloalcényle

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5052019A (fr) * 1973-09-13 1975-05-09
US20050113609A1 (en) * 2002-07-03 2005-05-26 Asahi Glass Company Limited Fluorine-containing unsaturated compound and method for its production
US20070299276A1 (en) * 2006-06-22 2007-12-27 Andrew Edward Feiring Preparation of fluoroalkoxystyrenes
US20140135518A1 (en) * 2012-11-14 2014-05-15 E I Du Pont De Nemours And Company Perfluoropolyvinyl modified aryl intermediates and monomers
WO2016032739A1 (fr) * 2014-08-27 2016-03-03 3M Innovative Properties Company Nouveaux alcènes polyfluoroalkylés et composés de silicium préparés à partir de ces derniers
WO2016096129A1 (fr) * 2014-12-19 2016-06-23 Merck Patent Gmbh Composés fluorés
WO2019049754A1 (fr) * 2017-09-05 2019-03-14 Ａｇｃ株式会社 Composé contenant du fluor, composition et article
WO2019067408A1 (fr) * 2017-09-27 2019-04-04 Arkema Inc. Polymères de (méth)acrylates d'éther d'haloalkyle et d'haloalcényle

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PLENKIEWICZ HALINA: "REAcTIoNs OF POLYFLUO- WITH EWOIATE ANIONS OF ALO", JOURNAL OF FLUORINE CHEMISTRY, 1 January 1987 (1987-01-01), pages 319 - 327, XP055872341, Retrieved from the Internet <URL:https://www.sciencedirect.com/science/article/pii/S0022113900820746?via%3Dihub> [retrieved on 20211213] *

Also Published As

Publication number Publication date
EP4211105A1 (fr) 2023-07-19
US20230365484A1 (en) 2023-11-16
KR20230065282A (ko) 2023-05-11
JP2023540369A (ja) 2023-09-22
CN116096697A (zh) 2023-05-09

Similar Documents

Publication Publication Date Title
US8669392B2 (en) Process for preparing 2,3-di-non-straight-alkyl-2-cyanosuccinic acid diesters
US20130253220A1 (en) Partially fluorinated sulfinic acid monomers and their salts
CN107787343A (zh) 生产具有氨基酸基团的有机硅化合物的方法
EP2321250B1 (fr) Procédé de fabrication d&#39;agents tensioactifs fluorés
KR100517039B1 (ko) 실란화된 (메트)아크릴레이트의 제조 방법
WO2022053420A1 (fr) Procédé de préparation de composés fluoroéthers à groupes terminaux insaturés
EP0972761B1 (fr) Sels de sulfonium et procédé pour leur préparation
EP0005094B1 (fr) Procédé de préparation de tris-(polyoxaalkyl)-amines
RU2540089C1 (ru) Способ получения 1-этил-3-[(оксифенил)метил]алюминациклопентанов
US7388103B2 (en) Cyclopentane carboxylate compounds, process and intermediates for preparing the same and use thereof
US3170913A (en) Azo-bis-alkylphosphonates and corresponding acids
US20070123731A1 (en) Process for preparing fluorinated alkyl carboxylate esters
KR20220073424A (ko) In-situ (메트)아크릴산 아릴 에스터의 제조 방법
EP1288184B1 (fr) Dérivé de bis(diphénylvinyl)arène
KR102371579B1 (ko) (메트)아크릴산 에스테르계 화합물 제조방법
US3663592A (en) Fluoroalkoxyalkyl 2-cyanoacetates
US3609163A (en) Process for preparing 5- vinyl-1,3,4-dioxcazol-2-ones
US4568759A (en) Preparation of epoxides
JP4937530B2 (ja) 含フッ素化合物及びその製造方法
Hasilov Study of synthesis and properties of differents of natural oil and some carbonic acids
JP4188060B2 (ja) １−置換フェニル−ω−ブロモアルカンの製造法
EP0272971A2 (fr) Di-bishydroxy de l&#39;acide cyanurique, ses dérivés trisubstitués et leur procédé de fabrication
SU349679A1 (ru) Способ получения
CN115947753A (zh) 一种bdp的制备方法
WO2015066018A1 (fr) Composés aryl-époxyde fluorés

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21773347

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2023515577

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20237010989

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2021773347

Country of ref document: EP

Effective date: 20230411